Orthochromatic polyester resin composition and molding product thereof

ABSTRACT

A tinted polyester resin composition having good color and useful for many uses (fibers, films and other formed articles) contains an aromatic polyester polymer and a tinting agent; the tinting agent is contained in a content of 0.1 to 10 ppm by mass in the composition, and has a maximum absorption wavelength in the range of from 540 to 600 nm in the absorption spectrum in the wavelength band of from 380 to 780 nm, determined in a solution of the tinting agent in a concentration of 20 mg/liter in chloroform in an optical path having a length of 1 cm; and ratios of optical absorbances A 400 , A 500 , A 600  and A 700  of visible light spectra at wavelengths of 400 nm, 500 nm, 600 nm and 700 nm respectively to an optical absorbance A max  in the visible light spectrum at the maximum absorption wavelength, determined in the above-mentioned chloroform solution at a optical path having a length of 1 cm, satisfy the requirements of 0.00≦A 400 /A max ≦0.20, 0.10≦A 500 /A max ≦0.70, 0.55≦A 600 /A max ≦1.00 and 0.00≦A 700 /A max ≦0.05.

TECHNICAL FIELD

The present invention relates to a tinted polyester resin compositionand a shaped article made thereof. More particularly, the presentinvention relates to a polyester resin composition, containing cobaltmetal element in an extremely small amount, tinted to a desired colortone and having an excellent formability and a shaped article thereof.

BACKGROUND ART

It is well known that polyester resins, particularly polyethyleneterephthalate, polyethylene naphthalate, polytrimethylene terephthalateand polytetramethylene terephthalate resins have excellent mechanical,physical and chemical performances and, therefore, are widely utilizedfor fibers, films and other shaped articles.

Among these polyesters, polyethylene terephthalate resin is usuallyproduced by a two step process. Namely, in the first step, an ethyleneglycol ester of terephthalic acid and/or a polymer with a low degree ofpolymerization produced by a method in which terephthalic acid andethylene glycol are directly subjected to a esterification reaction; ora method in which a lower alkyl ester of terephthalic acid, for example,dimethyl terephthalate, and ethylene glycol are subjected to atransesterification reaction, or a method in which terephthalic acid andethylene oxide are reacted with each other; and then in a second step,the reaction product of the first step is subjected to apolycondensation reaction in the presence of a polymerization catalyst,while heating the reaction mixture under a reduced pressure with thepolymerization degree of the resultant product reached a desired level,to produce the target polyethylene terephthalate.

It is well known that, in the polyester resin produced by theabove-mentioned process, the reaction rate and the quality of theresultant polyester resin greatly depend on the type of the catalystused in the polycondensation step. With respect to the above-mentioneddependency, it is also known from the previous research results thatwhen a catalyst comprising an antimony compound or a germanium compoundwhich has been widely used as a polycondensation catalyst, is used, thepolycondensation can be carried out at an excellent efficiency and theresultant polyester resin exhibits a good color tone.

However, when continuous melt spinning of a polyester produced by usingan antimony compound as a polycondensation catalyst is carried out overa long period of time, there arises the problems that foreign matteradheres and is deposited around a spinneret for melt spinning. Thisforeign matter may be referred to as spinneret foreign matterhereinafter. The deposited foreign matter causes a bending phenomenon ofthe molten polyester streams extruded from the spinneret, which leads tothe decrease in formability of the polymer melt and the occurrence offuzz and/or breakage of filament yarns obtained in the melt-spinning anddrawing steps.

Generally, as catalysts for the polyester usable for PET bottles, etc.,germanium compounds are used. In this connection, there are problemsthat germanium is a rare metal and is expensive and, thus, the resultantresin products are also expensive.

There has been proposed to use, as other polycondensation catalyst thanthe antimony compounds and the germanium compounds, titanium compounds,for example, titanium tetrabutoxide. When titanium compounds are used,the above-mentioned problems on the formability of the polyester melt,derived from the deposition of the spinneret foreign matter, can besolved. However, another problems, that the resultant polyester resin iscolored yellowish and exhibits an insufficient thermal stability of thepolyester melt, occur.

For example, Japanese Examined Patent Publications No. 48-2229 (PatentReference 1) and No. 47-26597 (Patent Reference 2) disclose that, astitanium compounds other than those mentioned above, titanium hydroxideor α-titanic acid is used as a catalyst for the production ofpolyesters. However, when titanium hydroxide is used, it is not easy topulverize titanium hydroxide, and when α-titanic acid is used, α-titanicacid has a low stability of the chemical structure thereof and, thus, isdifficult to preserve and handle. Therefore, these titanium componentsare not appropriate to use for industrial practice, and hardly produce apolyester polymer having a good color (b value).

To solve the above-mentioned problems, there have been attempted to usea product obtained by a reaction of a titanium compound with a specificphosphorus compound as disclosed in WO 01/00706 (Patent Reference 3) andWO 03/008479 (Patent Reference 4), and a non-reacted mixture or areaction compound of a titanium component with a specific phosphoruscompound as disclosed in WO 03/027166 (Patent Reference 5), as acatalyst for the production of the polyester polymer. It is true thatthe above-mentioned catalysts contribute to enhancing the thermalstability of the polyester melt and to improving the color of theresultant polymer. However, these catalyst cause the reaction rate inthe production of the polyester to be low, and thus a problem, that theproductivity of the polyester is somewhat low, occurs.

For the purpose of enhancing the stable formability of the polyester themethod in which no antimony is used is an effective means. However, theno-antimony method causes the color of the resultant polymer and polymerproducts to be unsatisfactory and thus has not been utilized inpractice. Therefore, a polyester produced by using a catalyst containingno antimony and having a good color is required.

In the production of the above-mentioned polyester, usually, thepolymerization temperature must be controlled to approximately from 280to 300° C. However, it is known that this high polymerizationtemperature causes a problem that the resultant polymer is discoloreddue to thermal decomposition of the polymer, namely, the polyester perse is colored yellow.

For the purpose of solving the yellow-coloring problem as mentionedabove, usually, a cobalt compound is mixed into the polyester polymer todecrease the yellow-coloring, as disclosed in, for example, JapaneseUnexamined Patent Publication No. 51-128397 (Patent Reference 6). Theaddition of the cobalt compound can certainly improve the color (bvalue) of the polyester polymer. However, the addition of the cobaltcompound causes a plurality of problems in that, regarding the thermalstability of the melt of the polyester polymer, the added cobaltcompound deposits in the polymer and causes foreign matter to begenerated, and the processability of the polyester polymer, to produce adesired shaped article, and the quality of the resultant shaped articleare probably affected. Further, in the case where a manganese compoundis used as a catalyst for the transesterification reaction, and a cobaltcompound is added, as a tinting agent, into the reaction mixture, theresultant polyester polymer has the problems that the cloths and fibersmade from the resultant polyester polymer may be discolored when treatedwith a bleaching agent.

Also, as an attempt of improving the color of the polyester polymer, apolyethylene naphthalate resin knead-mixed with a dye is disclosed in,for example, Japanese Unexamined Patent Publication No. 11-158257(Patent Reference 7), Japanese Unexamined Patent Publication No.3-231918 (Patent Reference 8), Japanese Unexamined Patent PublicationNo. 11-158257 (Patent Reference 9) and Japanese Unexamined PatentPublication No. 11-158361 (Patent Reference 10).

Reference List

-   -   Patent Reference 1 JP-48-2229-B    -   Patent Reference 2 JP-47-26597-B    -   Patent Reference 3 WO 01/00706 pamphlet    -   Patent Reference 4 WO 03/008479 pamphlet    -   Patent Reference 5 WO 03/027166 pamphlet    -   Patent Reference 6 JP-51-128397-A    -   Patent Reference 7 JP-11-158257-A    -   Patent Reference 8 JP-3-231918-A    -   Patent Reference 9 JP-11-158257-A    -   Patent Reference 10 JP-11-158361-A

DISCLOSURE OF THE INVENTION

An object of the present invention is to provide a tinted polyesterresin composition having a good white color, substantially no or littlegeneration of foreign matter adhered to a shaping orifices or dies evenwhen a shaping process, for example, fiber-forming process orfilm-forming process is continuously carried out over a long period oftime, and a good formability, and a shaped article produced from thetinted polyester resin composition and having a good appearance.

The above-mentioned object can be attained by the tinted polyester resincomposition of the present invention and a shaped article made from thesame.

The tinted polyester resin composition of the present inventioncomprises an aromatic polyester polymer and a tinting agent, wherein

(a) the tinting agent is present in a content of 0.1 to 10 ppm by mass,

(b) a maximum absorption wavelength of the tinting5 agent in anabsorption spectrum in the wavelength range of 380 to 780 nm is in therange of 540 to 600 nm, determined in a chloroform solution of thetinting agent in a concentration of 20 mg/liter and over an optical pathhaving a length of 1 cm, and

(c) ratios of optical absorbances A₄₀₀, A₄₀₀, A₅₀₀, A₆₀₀ and A₇₀₀ ofvisible light spectra at wavelengths of 400 nm, 500 nm, 600 nm and 700nm respectively to an optical absorbance A_(max) in the visible lightspectrum at the maximum absorption wavelength, of the tinting agent,determined in the above-mentioned chloroform solution of the tintingagent at the optical path having a length of 1 cm, satisfy therequirements (1) to (4):0.00≦A ₄₀₀ /A _(max)≦0.20  (1)0.10≦A ₅₀₀ /A _(max)≦0.70  (2)0.55≦A ₆₀₀ /A _(max)≦1.00  (3)0.00≦A ₇₀₀ /A _(max)≦0.05  (4)

In the tinted aromatic polyester resin composition of present invention,the tinting agent is preferably selected from tinting coloring mattershaving a mass reduction-initiating temperature of 250° C. or more,determined by heating the coloring matters in a nitrogen gas atmosphereat a temperature-increasing rate of 10° C./minute while measuring themass of the coloring matters by using a thermobalance.

In the tinted aromatic polyester resin composition of the presentinvention, the cobalt metal element in the composition is preferablypresent in a content controlled to 10 ppm by mass or less on the basisof the mass of the composition.

In the tinted aromatic polyester resin composition of the presentinvention, a metal element having a true specific gravity of 5.0 or morein the composition is preferably present in a content controlled to 10ppm by mass on the basis of the mass of the composition.

In the tinted aromatic polyester resin composition of the presentinvention, the aromatic polyester polymer is preferably one produced byusing a catalyst comprising at least one member selected from titaniumcompounds and aluminum compounds.

In the tinted aromatic polyester resin composition of the presentinvention, preferably, the aromatic polyester polymer is one produced byusing a catalyst comprising at least one member selected from titaniumcompounds and phosphorus compounds; a molor ratio of phosphorus atoms totitanium atoms contained in the catalyst satisfies the requirement (5):1≦M _(P) /M _(Ti)≦15  (5)wherein M_(P) and M_(Ti) respectively represent contents in millimolesof phosphorus element and titanium atoms contained in the aromaticpolyester polymer; and the molar amount of the titanium metal element inthe residual catalyst dissolved and contained in the polyester resincomposition is in the range of 2×10⁻³ to 15×10⁻³% on the basis of themolar amount of all dicarboxylic acids continued, as apolyester-constituting component, in the above-mentioned polymer.

In the tinted aromatic polyester resin composition of the presentinvention, the aromatic polyester polymer preferably comprises, as aprincipal component, at least one member selected from the groupconsisting of polyethylene terephthalate, polyethylene naphthalate,polytrimethylene terephthalate, polytrimethylene naphthalate,polytetramethylene terephthalate and polytetramethylene naphthalate.

In the tinted aromatic polyester resin composition of the presentinvention, the tinting agent preferably comprises a blue color-tintingcoloring matter and a violet color-tinting coloring matter in a massratio in the range of from 90:10 to 40:60.

In the tinted aromatic polyester resin composition of the presentinvention, the tinting agent preferably comprises a blue color-tintingcoloring matter and a red or orange color-tinting coloring matter in amass ratio in the range of from 98:2 to 80:20.

In the tinted aromatic polyester resin composition of the presentinvention, the tinting agent is preferably one mixed, at one or morestages in the production procedure of the aromatic polyester polymer,into a reaction mixture in the production procedure.

In the tinted aromatic polyester resin composition of the presentinvention, the tinting agent is preferably one knead-mixed into thearomatic polyester polymer in the state of a melt.

The tinted and shaped polyester resin article of the present inventionis one produced from the tinted polyester resin composition as definedin any one of claims 1 to 11.

In the tinted and shaped polyester resin article of the presentinvention, the article is preferably selected from fiber products.

In the tinted and shaped polyester resin article of the presentinvention, the article is preferably selected from film products.

In the tinted and shaped polyester resin article of the presentinvention, the article is preferably selected from bottle products.

The polyester resin composition of the present invention is one tintedwith a specific tinting agent having been a specific tinting effect,thus has a good color even in the case where the polyester resincomposition having been prepared from a polyester resin produced withoutusing a catalyst containing antimony or germanium, and can provide ashaped article having a bright color.

The tinted polyester resin composition of the present invention cansolve the defects, namely an degradation in color (increases in a* valueand b* value), of the polyester produced in the presence of aconventional catalyst containing no antimony and no germanium, whilemaintaining the excellent formability and mechanical and chemicalperformances unchanged. Therefore, the shaped articles, for example,fibers and films, produced from the polyester resin composition of thepresent invention, have a good color and are highly useful in practice.

BEST MODE FOR CARRYING OUT THE INVENTION

The polyester resin composition of the present invention comprises anaromatic polyester polymer and a tinting agent.

The aromatic polyester polymer usable for the present invention isobtained by a polycondensation reaction of an aromatic dicarboxylic acidcomponent with a glycol component. The aromatic dicarboxylic acidcomponent preferably comprises, as a principal component, for example, amember selected from terephthalic acid, naphthalene dicarboxylic acidand ester-forming derivatives of the acids (for example, di(lower alkyl)diesters, etc.). The glycol component comprises, as a principalcomponent, a member selected from, for example, ethylene glycol,trimethylene glycol and tetramethylene glycol. The aromatic dicarboxylicacid component and the glycol component may comprise, in addition to theabove-mentioned principal components, one or more copolymerizationcomponents selected from, for example, isophthalic acid, aliphaticdicarboxylic acids (for example, adipic acid, etc.), aromaticdihydroxyle compounds, (for example, bisphenol A, etc.) andhydroxycarboxylic acids (for example, hydroxybenzoic acid, etc.).

The above-mentioned aromatic polyester polymer preferably comprises, asa principal constitutional component, at least one member selected fromthe group consisting of polyethylene terephthalate, polyethylenenaphthalate, polytrimethylene terephthalate, polytrimethylenenaphthalate, polytetramethylene terephthalate and polytetramethylenenaphthalates. Among them, the polyethylene terephthalate is preferablycontained as a principal constitutional component in the aromaticpolyester polymer. The term “a principal constitutional component”refers to a component in an amount corresponding to 80 molar % or moreof the total amount of all the repeating units, of the aromaticpolyester polymer.

In the polyester resin composition of the present invention, the contentof metal elements having a true specific gravity of 5.0 or more, basedon the mass of the resin composition, is preferably controlled to alevel of 10 ppm or less by mass.

The metal elements having a true specific gravity of 5.0 or more areusually derived from metallic compounds contained in catalyst, metallictinting agents, and delustering agents which are contained in thepolyester polymer. In concrete terms, the metal elements includeantimony, germanium, manganese, cobalt, cerium, tin, zinc, lead, andcadmium. However, the metal elements having a true specific gravity of5.0 or more do not include titanium, aluminum, calcium, magnesium,sodium and potassium.

The influence of the metal elements on the polyester resin compositionof the present invention varies in response to the type of the metalcontained in the polyester resin composition. For example, in the casewhere the content of antimony metal is more than 10 ppm by mass, foreignmatter is generated in a melt-spinning procedure or a film-formingprocedure and adhere around a spinning orifices or extruding dies so asto affect on the continuous formability over a long period. In the caseof germanium, the metal per se is expensive and a high content thereofcauses the resultant polyester resin composition to have an increasedprice. Also, in the case of lead or cadmium, the metal per se ispoisonous and a high content of a poisonous metal in the polyesterpolymer is not preferable. The content of the high specific gravitymetal element in the polyester resin composition is preferably 0 to 7ppm by mass, more preferably 0 to 5 ppm by mass.

In the polyester resin composition of the present invention, the contentof the cobalt compound, in terms of cobalt metal element, is preferablycontrolled to 10 ppm by mass or less, more preferably 0 to 7 ppm bymass, on the basis of the mass of the polyester resin composition. Thecobalt compound contributes to improving the color of the polyesterresin. However, in the case where the content of the cobalt metalelement exceeds 10 ppm by mass, the resultant polyester resincomposition may exhibit insufficient heat resistance and melt stabilityand thus may be thermally decomposed in the melt spinning. The thermaldecomposition product of the cobalt compound may cause the resultantpolyester resin composition and the shaped article from the resincomposition to exhibit degraded qualities.

The polyester resin composition of the present invention contains thetinting agent in an amount of 0.1 to 10 ppm by mass on the basis of themass of the polyester resin composition. The tinting agent usable forthe polyester resin composition of the present invention includesorganic polycyclic aromatic dyes, organic solvent-soluble coloringmatters for example, oil-soluble dyes, and pigments. In concrete terms,the tinting agent for the present invention include blue color-tintingcoloring matters, violet color-tinting coloring matters, redcolor-tinting coloring matters, and orange color-tinting coloringmatters which will be explained hereinafter. These coloring matters fortinting may be used alone or in a mixture of two or more thereof.

Among them, the mixtures of two or more coloring matters for tinting ispreferably utilized due to the fact that the coloring matter mixturesfor tinting easily satisfy the requirements concerning the opticalabsorption spectra of the tinting agent.

For the tinting agent for the present invention, the organicsolvent-soluble coloring matters, particularly oil-soluble dyes arepreferably used. The blue tinting coloring matters include, for example,C.I. Solvent Blue 11, C.I. Solvent Blue 25, C.I. Solvent Blue 35, C.I.Solvent Blue 36, C.I. Solvent Blue 45 (Telasol Blue RLS), C.I. SolventBlue 55, C.I. Solvent Blue 63, C.I. Solvent Blue 78, C.I. Solvent Blue83, C.I. Solvent Blue 87 and C.I. Solvent Blue 94; the violet tintingcoloring matters include, for example, C.I. Solvent Violet 8, C.I.Solvent Violet 13, C.I. Solvent Violet 14, C.I. Solvent Violet 21, C.I.Solvent Violet 27, C.I. Solvent Violet 28, and C.I. Solvent Violet 36;the red tinting coloring matters include, for example, C.I. Solvent Red24, C.I. Solvent Red 25, C.I. Solvent Red 27, C.I. Solvent Red 30, C.I.Solvent Red 49, C.I. Solvent Red 52, C.I. Solvent Red 100, C.I. SolventRed 109, C.I. Solvent Red 111, C.I. Solvent Red 121, C.I. Solvent Red135, C.I. Solvent Red 168, and C.I. Solvent Red 179; and the orangecolor tinting coloring matters include, for example, C.I. Solvent Orange60, etc.

The tinting agent contained in the polyester resin composition of thepresent invention has a maximum absorption wavelength in the range of540 to 600 nm in an absorption spectrum in the wavelength range of 380to 780 nm determined in a chloroform solution of the tinting agent in aconcentration of 20 mg/liter at an optical path having a length of 1 cm,and has ratios of optical absorbances A₄₀₀, A₅₀₀, A₆₀₀ and A₇₀₀ ofvisible light spectra at wavelength of 400 nm, 500 nm, 600 nm and 700 nmrespectively to an optical absorbance A_(max) in the visible lightspectrum at the maximum absorption wavelength, determined in theabove-mentioned chloroform solution of the tinting agent at the opticalpath having a length of 1 cm, and satisfying the requirements (1) to(4):0.00≦A ₄₀₀ /A _(max)≦0.20  (1)0.10≦A ₅₀₀ /A _(max)0.70  (2)0.55≦A ₆₀₀ /A _(max)1.00  (3)0.00≦A ₇₀₀ /A _(max)0.05  (4)

In the requirements (1) to (4), A₄₀₀, A₅₀₀, A₆₀₀, and A₇₀₀ respectivelyrepresent optical absorbances in the visible light absorption spectra atwavelength of 400 nm, 500 nm, 600 nm and 700 nm, and A_(max) representsan optical absorbance in the visible light absorption spectrum at amaximum absorption wavelength.

The absorption spectrum refers to a spectrum measured by a usualspectrophotometer. In the case where the maximum absorption wavelengthin the absorption spectrum of the solution of the tinting agentcontained in the polyester resin composition is less than 540 nm, theresultant polyester resin composition exhibits too deep a reddish colortone and thus is not preferable, and where the maximum absorptionwavelength is more than 600 nm, the resultant polyester resincomposition exhibits too deep a bluish color tone, and thus is notpreferable.

The maximum absorption wavelength is preferably in the range of from 545to 595 nm, more preferably from 550 to 590 nm.

In the case wherein the optical path having a length of 1 cm of thechloroform solution of the tinting agent usable for the polyester resincomposition of the present invention in a concentration at 20 mg/liter,the ratios of the absorptions at the wavelengths as mentioned above tothe absorption at the maximum absorption wavelength do not satisfy atleast one of the above-mentioned requirements (1) to (4), the resultantpolyester resin composition exhibit too deep tinted color tone.

The values of A₄₀₀/A_(max), A₅₀₀/A_(max), A₆₀₀/A_(max), and A₇₀₀/A_(max)satisfying the requirements (1) to (4) are preferably in the rangespecified by the equations (6) to (9):0.00≦A ₄₀₀ /A _(max)≦0.15  (6)0.30≦A ₅₀₀ /A _(max)≦0.60  (7)0.60≦A ₆₀₀ /A _(max)≦0.95  (8)0.00≦A ₇₀₀ /A _(max)≦0.03  (9)in which equations, A₄₀₀, A₅₀₀, A₆₀₀, and A₇₀₀ are as defined above.

In the polyester resin composition of the present invention, if thecontent of the above-mentioned tinting agent contained therein is lessthan 0.1 ppm by mass, the resultant polyester resin composition exhibitstoo deep a yellowish color tone.

Also, if the tinting agent content is more than 10 ppm by mass, theresultant polyester resin composition exhibits a decreased lightness andan increased grayish color tone and thus is not preferable.

The content of the tinting agent is preferably in the range of from 0.3ppm by mass to 9 ppm by mass, more preferably from 0.5 ppm by mass to 8ppm by mass.

The apparent white color of the polyester resin composition of thepresent invention is controlled by the tinting agent. Namely,preferably, in the L* a* b* color specification system, the polyesterresin composition heat-treated at a temperature of 140° C. for 2 hoursto crystallize the resin, the a* value is in the range of from −9 to 0,and the color b* value is in the range of from −2 to +10. The a* valueand the b* value of the resin composition vary in response to the amountof the tinting agent. If the a* value is less than −9, the resultantpolyester resin composition exhibits too deep a greenish color tone, andif the a* value is more than 0, the resultant polyester resincomposition exhibits too deep a reddish color tone, and thus is notpreferable. Also, if the b* value is less than −2, the resultantpolyester resin composition exhibits too deep a bluish color tone and ifit is more than +10, the resultant polyester resin composition exhibitstoo deep a yellowish color tone, and thus is not preferable. The a*value is in more preferably the range of from −8 to −1, still morepreferably from −7.5 to −2. Also, the b* value is more preferably in therange of from −1 to +9, still more preferably from 0 to 8.

The tinting agent for the polyester resin composition of the presentinvention preferably has a mass reduction-initiating temperature (T₁) of250° C. or more, determined by heating the tinting agent in a nitrogengas atmosphere at a temperature-increasing rate of 10° C./minute whilemeasuring the mass of the tinting agent by using a thermobalance, inaccordance with JIS K 7120. The mass reduction-initiating temperature isan indicator of heat resistance which is provided on the tinting agent.If the mass reduction-initiating temperature of the tinting agent isless than 250° C. or less, this tinting agent may have an insufficientheat resistance, and thus may cause the finally resultant polyesterresin composition to be discolored.

The mass reduction-initiating temperature is more preferably 300° C. ormore but not more that 500° C. More preferably, the tinting agent is notdecomposed at a temperature at which the aromatic polyester polymer isin the state of a melt.

There is no specific limitation to the process for producing thearomatic polyester polymer contained in the polyester resin compositionof the present invention, and thus the aromatic polyester polymer can beproduced by the conventional production processes.

Namely, first, a glycol ester of a dicarboxylic acid and/or an oligomerthereof is produced by a direct esterification reaction of thedicarboxylic acid component comprising, for example, terephthalic acidwith a glycol component comprising, for example, ethylene glycol, or atransesterification reaction of a di(lower alkyl)diester of adicarboxylic acid component, for example, dimethyl terephthalate, with aglycol component comprising, for example, ethylene glycol. Then thereaction product is subjected to a poly-condensation reaction in thepresence of a polymerization catalyst by heating the reaction productunder a reduced pressure until the degree of polymerization reaches thedesired degree, to produce the target aromatic polyester polymer. In thecase where a polyester structure other than the that of the aromaticpolyester polymer is contained as a copolymerization component, a methodin which the aromatic polyester component and the copolymerizationcomponent are copolymerized or another method in which theabove-mentioned two different types of the polyesters are produced by aknown process, and then the resultant polyesters are blended to eachother, can be utilized.

The aromatic polyester polymer usable for the polyester resincomposition of the present invention includes the polymers produced byusing a catalyst containing at least one compound selected from titaniumcompounds and aluminum compounds. There is no specific limitation to thetype of the titanium compounds. Namely, the titanium compounds includeusual titanium compounds usable as a polycondensation catalyst forpolyesters, for example, titanium acetate and tetra-n-butoxytitanium.

Preferably, the titanium compounds are selected from the compoundsrepresented by the general formula (I) shown below, reaction product ofthe compounds represented by the general formula (I) with the aromaticpolycarboxylic acids represented by the general formula (II) as shownbelow or anhydrides of the acids, and the compounds represented by thegeneral formula (III) shown below.

In the formula (I), R¹, R², R³ and R⁴ respectively and independentlyfrom each other represent an alkyl group or a phenyl group, m representsan integer of 1 to 4, when m is 2, 3 or 4, two, three or four R² and R³may be the same as each other or different from each other. Theabove-mentioned alkyl group preferably contains 1 to 10 carbon atoms,more preferably 1 to 6 carbon atoms.

In the formula (II), q represents an integer of 2 to

In the formula (III), X represents an alkyl or alkoxy group having 1 to20 carbon atoms or an aryl or aryloxy group having 6 to 20 carbon atoms.

There is no specific limitation to the types of the aluminum compoundfor the polycondensation catalyst. For example, aluminum acetylacetonatehas a high stability and is easily handled and is excellent as acatalyst.

The above-mentioned titanium compounds and the aluminum compounds may beused alone or in a mixture of two or more thereof. Particularly andpreferably, the titanium compound is used alone.

Even in the case where the compounds represented by the general formula(I), the reaction products of the compounds represented by the generalformula (I) with the aromatic polycarboxylic acids represented by thegeneral formula (II) or anhydrides of the acids, and the compoundsrepresented by the general formula (III) are used alone, a good resultcan be obtained.

Also, as a catalyst for the production of the aromatic polyesterpolymer, antimony compounds and/or germanium compounds can be used.There is no specific limitation to the type of the antimony compoundsand the germanium compounds, and conventional antimony compounds andgermanium compound as polymerization catalyst for polyesters can be usedfor the polyester polymer of the present invention. For example,diantimony trioxide, antimony acetate, antimony pentachloride, germaniumdioxide or germanium tetralkoxides can be utilized. Among them,diantimony trioxide and/or germanium dioxide is preferably utilized.

Regarding the titanium tetraalkoxides and/or the titanium tetraphenoxiderepresented by the general formula (I), there is no specific limitationas long as each of R¹ to R⁴is an alkyl group and/or a phenyl group, andtitanium tetraisoproxide, titanium tetra-n-propoxide, titaniumtetra-n-butoxide, titanium tetraethoxide and titanium tetraphenoxide arepreferably utilized. The aromatic polycarboxylic acid represened by thegeneral formula (II) and anhydrides thereof to be reacted with theabove-mentioned titanium compounds, preferably include phthalic acid,trimellitic acid, hemimellitic acid and pyromellitic acid and anhydridesof the above-mentioned acids.

The reaction of the above-mentioned titanium compounds with the aromaticpolycarboxylic acids or anhydrides thereof is carried out by, forexample, the following procedure. Namely, an aromatic polycarboxylicacid or anhydride thereof is entirely or partially dissolved in asolvent; into the resultant solution, a titanium compound is addeddropwise and the resultant mixture is subjected to a reaction at atemperature of from 0 to 200° C. for 30 minutes. Also, optionally, afterthe dropwise addition of the titanium compound, the remaining amount ofthe aromatic polycarboxylic acid or anhydride thereof is mixed into themixture. Further, the compounds represented by the general formula (III)can be produced by reacting the compounds represented by the generalformula (I) with a monoalkyl phosphonic acid, a monoarylphosphonic acid,a monoalkyl phosphate or a monoaryl phosphate at a temperature in therange of from 70 to 150° C.

In the polyester resin composition of the present invention, preferably,the aromatic polyester polymer is one produced by using a catalystcomprising a titanium compound and a phosphorus compound, the molarratio of phosphorus element to titanium metal element contained in theabove-mentioned catalyst satisfies the following equation (5):1≦M _(P) /M _(Ti)≦15  (5)in which equation (5) M_(P) and M_(Ti) respectively representconcentrations in millimoles of phosphorus element and titanium metalelement contained in the aromatic polyester polymer; and the molaramount of titanium metal element in the residual catalyst dissolved andcontained in the polyester resin composition comprising the aromaticpolyester polymer corresponds to 2×10⁻³ to 15×10⁻³% of the molar amountof all the dicarboxylic acids contained, as a polymer-constitutingcomponent, in the above-mentioned polymer.

It should be noted that the amount of titanium metal element containedin the aromatic polyester polymer and derived from the titaniumcompounds soluble in the polyester polymer does not include the amountof titanium metal element derived from inorganic titanium compounds, forexample, titanium dioxide, insoluble in the polyester polymer, and islimited to the amount of titanium metal element derived from organictitanium compounds which are usually used as a catalyst and organictitanium compounds continued, as impurities, titanium oxide used as adelustering agent. In the case where the above-mentioned amount of thetitanium metal element is less than 2×10⁻³%, the polycondensationreaction may not be sufficiently proceeded. Also, if the amount is morethan 5×10⁻³%, the resultant polyester resin composition may have ayellowish color tone, and exhibit a decreased heat resistance.

The content of the titanium metal element is more preferably in therange of from 3×10⁻³ to 10×10⁻³%. Also, in the case where the molarratio M_(P)/M_(Ti) of phosphorus element to titanium metal elementderived from the compounds soluble in the aromatic polyester polymercontained in the polymer is less than 1, the resultant polyester resincompound has a yellowish color tone and, if the ratio is more than 15,the catalyst causes the polycondensation reaction to be carried out at aslow rate. The ratio M_(P)M_(Ti) is preferably in the range of from 2 ormore to not more than 10.

To keep the amounts of the titanium metal element and the phosphoruselement derived from the compounds soluble in the polyester contained inthe polyester resin composition in a preferable ratio, the phophoruscompound is mixed into the polyester resin composition produced in thepresence of a titanium-containing catalyst. Otherwise, the preferableratio can be attained by, for example, using, as a catalyst, thecompound represented by the above-mentioned general formula (III). Thereis no limitation to the compounds of the formula (III). More preferably,the compounds of the formula (III) is selected from phosphoric acid,phosphorous acid, phosphonic acid, phosphinic acid and alkyl esters,aryl esters and phosphonoacetates of the above-mentioned acids. Themixing of the above-mentioned phosphorus compound into the polyesterresin composition may be carried out at any stage as long as, after thetransesterification reaction or the esterification reaction, thereaction is substantially completed. Usually, it is preferred that themixing is carried out immediate after the esterification or thetransesterification reaction is completed, and then the resultantmixture is subjected to the polycondensation reaction.

There is no specific limitation to the intrinsic viscosity of thepolyester resin composition (determined in a solvent consisting ofortho-chlocophenol at a temperature of 35° C.). Preferably, theintrinsic viscosity is in the range in which the resultant polyesterresin composition can be used for conventional fibers, films and shapedarticles, for example, bottles, in concrete term, within the range offrom 0.40 to 1.00. Also, the polyester resin composition of the presentinvention is preferably selected from those having an intrinsicincreased viscosity by a solid phase polymerization.

The polyester resin composition of the present invention optionallycontains an additive, for example, a lubricant, an antioxidant, a solidphase polymerization accelerator, a fluorescent brightening agent, anantistatic agent, an antibacterial agent, ultraviolet ray-absorber,light stabilizer, thermostabilizer, light screening agent, anddelustering agent. For example, the delustering agent, for example,titanium dioxide and the antioxidant are preferably contained in thecomposition. These additives is preferably used in a small amount,preferably and the contents of metals having a true specific gravity of5.0 or more and halogen elements are preferably very small. As anantioxidant, hindered phenolic antioxidants are preferably employed. Inconcrete terms, the hindered phenolic antioxidants includepentaerythritol-tetrakis,[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspyro[5,5]undecane,1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzene)isophthalic acid,triethylglycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate],1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],2,2-thio-diethylene-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],octadecyl-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], etc. Thehindered phenolic antioxidant is preferably contained in a content of 1%by mass or less on the basis of the polyester resin composition. If thecontent of the antioxidant is more than 1% by mass, it may causegeneration of foreign matter during the forming procedure. Also, whenthe content of the antioxidant is more than 1% by mass, the meltstability-enhancing effect of the antioxidant may be saturated.

More preferably, the content of the hindered phenolic antioxidants is inthe range of 0.005 to 0.5% by mass. Also, the hindered phenolicantioxidants may be employed in combination with thioether compoundsecondary antioxidants. There is no specific limitation to the method ofmixing the antioxidants with the polyester resin composition. Theantioxidant may be contained in the polyester resin composite at anystages in the above-mentioned production procedure of the aromaticpolyester polymer or the production procedure of the polyester resincomposition which procedure will be explained hereinafter, for example,at a stage at which a tinting agent is imparted. Preferably, theantioxidant is mixed at least one stage of the production procedure ofthe aromatic polyester polymer, for example, at an appropriate stageafter the transesterification reaction or the esterification reactionwas completed but before the polymerization reaction is completed, intothe reaction mixture.

In the production of the polyester resin composition of the presentinvention, the above-mentioned tinting agent is preferably added, at atleast one stage of the production procedure of the aromatic polyesterpolymer, to a reaction mixture thereof. Among the stages at which thetinting agent is added, preferably, the addition of the tinting agent iscarried out at appropriate stages until the polymerization reaction iscompleted, more preferably after the transesterification or theesterification reaction is completed, and the tinting agent is mixedinto the resultant reaction mixture and then the tintingagent-containing reaction mixture is subjected to the polycondensationreaction. Otherwise, the tinting agent may be knead-mixed into thearomatic polyester polymer while the polymer is in the state of a melt.

In the production of the polyester resin composition of the presentinvention, preferably, a tinting agent comprising a mixture of a bluecolor-tinting coloring matter with a violet color-tinting coloringmatter in a mass ratio in the range of from 90:10 to 40:60 is used, or atinting agent comprising a mixture of a blue color-tinting coloringmatter with a red or orange color-tinting coloring matter in a massratio in the range of from 98:2 to 80:20 is used. Here, the bluecolor-tinting coloring matters are referred to as trade-availablecoloring matters for tinting which are indicated in a color name of“blue”. In concrete terms, the coloring matters having a maximumabsorption wavelength of about 580 to 620 nm in a visible light spectrummeasured in a solution of the coloring matter in a solvent arepreferably employed. Also, the violet color-tinting coloring matters arereferred to as trade-available coloring matters for tinting which areindicated in a color name of “violet”. In concrete terms, the coloringmatters having a maximum absorption wavelength of about 560 to 580 nm ina visible light spectrum measured in a solution of the coloring matterin a solvent are preferably employed. The red color-tinting coloringmatters are referred to as trade-available coloring matters for tintingwhich are indicated in a color name of “red”. In concrete terms, thecoloring matters having a maximum absorption wavelength of about 480 to520 nm in a visible light spectrum measured in a solution of thecoloring matter in a solvent are preferably employed. Also, the orangecolor-tinting coloring matters are referred to as trade-availablecoloring matters for tinting which are indicated in a color name of“orange”.

In the case where a blue color-tinting coloring matter is employed incombination with a violet color-tinting coloring matter, if the massratio. of the blue color-tinting coloring matter to the violetcolor-tinting coloring matter is more than 90:10, the resultantpolyester resin composition has a decreased a* value and exhibits agreenish color tone. Also, the blue color-tinting coloring matter isused in a mass ratio less than 40:60, the resultant polyester resincomposition may have a high a* value and exhibit a reddish color tone.Also, in the case where a blue color-tinting coloring matter is employedin combination with a red or orange color-tinting coloring matter, ifthe mass ratio of the blue color-tinting coloring matter to the combinedcoloring matter is more than 98:2, the resultant polyester resincomposition has a decreased a* value and exhibits a greenish color tone,and if the mass ratio is less than 80:20, the a* value increases and thecolor of the resin composition becomes reddish.

More preferably, the tinting agent comprises a combination of a bluecolor-tinting coloring matter with a violet color-tinting coloringmatter in a mass ratio in the range of from 80:20 to 50:50, or acombination of a blue color-tinting coloring matter with a red or orangecolor-tinting coloring matter in a mass ratio in the range of from 95:5to 90:10.

The tinted polyester resin composition of the present invention can beformed into formation-processed products of the tinted polyester resincomposition having a desired form and dimensions. Theformation-processed products include fiber articles, film articles andother shaped articles, for example, bottle articles and injection-moldedarticles.

There is no specific limitation to the process for producing the fiberarticles from the polyester resin composition of the present invention,and a conventional melt-spinning process can be utilized. For example,preferably a dried polyester resin composition is melt-spun at atemperature of 270 to 300° C., and the resultant melt-spun filaments aretaken up at a speed of 400 to 5000 m/minute. When the melt-spinningspeed is within the above-mentioned range, the resultant filaments havea satisfactory mechanical strength and can be wound up with a highstability. There is no specific limitation to the form of themelt-spinning orifices, and the orifices may have a circular, irregular,non-hollow or hollow forms. Also, the undrawn filaments produced in theabove-mentioned melt-spinning step are drawn. The drawing procedure maybe applied to the undrawn filaments after the filaments are wound up.Otherwise, the melt-spinning and drawing procedures may be continuouslycarried out without winding the undrawn filaments. Further, to improvethe hand of the polyester fiber articles of the present invention, andalkali-treatment may be applied to the polyester fiber articles.

There is no specific limitation to the process for producing thepolyester film articles of the present invention, and the film articlescan be produced by conventional melt film-forming processes. Forexample, a dried tinted polyester resin composition is melted at atemperature in the range of from 270° C. to 300° C., extruded into afilm form, and cooled on a cooling drum to prepare an undrawn film.

Then the undrawn film is biaxially drawn, heat-set, and optionallyheat-relaxed. In this case, the properties of the film articles, forexample, surface properties, density and thermal shrinkage, vary inresponse to the process conditions, for example, drawing conditions,etc. Therefore, the process conditions should be appropriatelyestablished.

The formation-processed articles of the polyester resin composition ofthe present invention include bottle articles and other injection-moldedarticles. There is no specific limitation to the process for producingthe formation-processed articles, and these articles may be produced byconventional melt-forming process. For example, a dried tinted polyesterresin composition is melted at a temperature of 270° C. to 300° C., andthe melt of the polyester resin composition is poured into a mold at atemperature of 0 to 80° C., to form molded articles.

In the production of the bottle articles, preferably a bottle preform isformed from the resin composition melt by using a mold for formingbottles and, then, the resultant preform is formed into a bottle form byusing a blow forming machine. In this connection, the bottle articlesinclude not only bottles but also bottle preforms.

EXAMPLES

The present invention will be illustrated by the following exampleswhich are not intended to restrict the scope of the present invention inany way. In the examples, intrinsic viscosity, color, titanium content,the height of adhered accumulation layers generated around the spinningorifices, etc. were determined by the following measurements.

(1) Intrinsic Viscosity

Chips of a polyester resin composition were dissolved inortho-chlorophenol by a dissolving operation at a temperature of 100° C.for 60 minutes. The intrinsic viscosity of the polyester resincomposition was calculated from a viscosity value of the dilutedsolution measured at a temperature of 35° C. by using the Ubbelohdeviscometer.

(2) Content of Diethyleneglycol

Chips of a polyester resin composition were decomposed with hydrazinehydrate, and the content of diethyleneglycol contained in the resultantdecomposition product was determined by using a gas chromatography(model: HP6850, made by Hewlett-Packard).

(3) Color (L* Value, a* Value and b* Value)

In the Case of Chips:

The chips of polyester resin composition were melted at a temperature of285° C. under vacuum for 10 minutes and the resultant melt was formed,on an aluminum plate, into a plate having a thickness of 3.0±1.0 mm, theresultant plate was rapidly cooled in ice water, and then the plate wassubjected to a drying-crystallization treatment at 140° C. for 2 hours.Thereafter, the resultant plate was placed on a white standard plate fordifferential colorimeter adjustment, and then the L* value and b* valueof the plate surface was measured in accordance with JIS Z 8729, byusing a Hunter differential colorimeter (model: CR-200) made by MinoltaK.K. The L* value represent a lightness of the color, and the larger theL* value, the higher the color lightness. The b* value represents adegree of discoloration of the polyester resin composition withyellowish color, which degree increases with increase in the b* value.

In the Case of Fibers:

Four tabular knitted fabrics were prepared from the fibers, andsuperimposed on each other. The L* value and the b* value of thesuperimposed fabrics were measured in the same manner as mentionedabove.

(4) Qualitative Analysis of Metal Components Having a True SpecificGravity of 5.0 or More

A sample of a polyester resin composition was mixed with ammoniumsulfate, sulfuric acid, nitric acid and perchloric acid and subjected toa wet decomposition treatment at approximately 300° C. for 9 hours. Theresultant decomposition liquid was diluted with water and then subjectedto a qualitative analysis using a ICP emission analysis apparatus(JY170, ULTRACE) made by RIGAKU DENKIKOGYO K.K., to confirm whether ornot the metal elements having a true specific gravity of 5.0 or morewere contained in the sample. With respect to the metal elements whichwere confirmed to be contained in contents of 1 ppm by mass or more, thecontents of the metal elements were recorded.

(5) Contents of Polyester-soluble Titanium, Aluminum, Antimony,Manganese, Germanium, Cobalt and Phosphorus

To determine the amounts of titanium element, aluminum element, antimonyelement, manganese element, germanium element, cobalt element andphosphorus element each soluble in a polyester contained in thepolyester resin composition, a sample in the form of particles of thepolyester resin composition was heat-melted on a steel plate andspecimens having a flat smooth surface was formed from the melt by suinga compressive press. The specimens were supplied to a fluorescent X-raytester (model: ZSX 100e, made by RIGAKU DENKIKOGYO K.K.), to determinethe contents of the above-mentioned elements. In the case where thepolyester resin composition contained titanium element derived fromtitanium dioxide added, as a delustering agent, to the polyester resincomposition, a sample of the polyester resin composition was dissolvedin ortho-chlorophenol, then an extraction treatment with a 0.5Nhydrochloric acid was applied to the dissolved polyester resincomposition, the resultant extraction liquid was subjected to aquantitative analysis using an electron spectrophotometer, model Z-8100,made by K.K. HITACHI SEISAKUSHO. When a dispersion of titanium dioxidein the extraction liquid prepared by the 0.5N hydrochloric acidextraction was observed, the dispersed titanium dioxide particles weredeposited by using a centrifugal separator, only the resultant clearsupernatant liquid was recovered by an inclination method, the recoveredliquid was subjected to the same measurement as mentioned above. Bythese testing operations, even when the polyester resin compositioncontained titanium dioxide derived from the delustering agent, thecontent of the titanium element derived from the polyester-solubletitanium compounds can be quantitatively determined.

(6) Height of Adhered Layers Formed Around Melt-spinning Orifices

The polyester resin composition for the testing was formed into chips,the chips were melted and extruded through a melt-spinneret having 12orifices each having a hole diameter of 0.15 mm. The melt-spinningprocedure was contained at a taking-up speed of 600 m/minute for twodays, the height of adhered layers formed around the outside edges ofthe orifices of the melt-spinneret was measured. The occurrences ofbending of the filamentary streams of the extruded melt of the polyesterresin component increases with increase in the height of the adheredlayer. Also, the greater the height of the adhered layer, the lower theformability of the polyester resin composition. Namely, the height ofthe adhered layer generated on the melt-spinneret is an indicator of theformability of the polyester resin composition.

(7) Haze

In the Case of Bottle Preform:

A testing sample was taken from a middle portion of a body portion of apreform in the longitudinal direction of the preform sampled frompreforms produced after the first five shots in the injection moltingprocedure. The haze of the taken portion of the preform sample wasmeasured by a haze meter (model: HDH-1001DP) made by NIHON DENSHOKUKOGYOK.K.

In the Case of Film:

A sheet of the polyester resin composition prepared by melt-extrudingthe resin composition onto a rotating cooling drum through amelt-extruder was rapidly cool-solidified to provide an undrawn film(sheet) having a thickness of 500 μm. The haze of the film was measuredby using a haze meter (model: HDH 1001DP) made by NIHON DESHOKUKOGYOK.K.

(8) Mass Reduction-initiating Temperature of Tinting Agent

A sample of the tinting agent was heated at a temperature-increasingrate of 10° C./minute in a nitrogen gas atmosphere and the massreduction-initiating temperature of the sample was measured by using athermobalance (model: TAS-200) made by RIGAKU DENKIKOGYO K.K., inaccordance with JIS K 7120.

Referential Example 1

Synthesis of Titanium Catalyst A

A solution of 0.2% by mass of trimellitic anhydride in ethylene glycolwas mixed with tetra-n-butoxytitanium in an amount of ½ mole per mole oftrimellitic anhydride. The mixture was subjected to a reaction for 60minutes by keeping it at a temperature of 80° C. in the air atmosphereunder the ambient atmospheric pressure. Then the resultant reactionmixture was cooled to room temperature, and the resultant catalyst wasrecrystallized with acetone in an amount of ten times the reactionmixture. The resultant precipitation was collected by filtration with afiltering paper, and dried at 100° C. for 2 hours, to obtain the desiredcompound. The resultant compound will be referred to as titaniumcatalyst A hereinafter.

Referential Example 2

Synthesis of Titanium Catalyst B

Mono-n-butyl phosphate in an amount of 3.5 parts by mass was dissolvedin 131 parts by mass of ethylene glycol by heating the mixture thereofat 120° C. for 10 minutes. The resultant ethylene glycol solution in anamount of 134.5 parts by mass was further mixed with 40 parts by mass ofethyleneglycol and in the resultant solution, 3.8 parts by mass oftetra-n-butoxytitanium were dissolved. The resultant reaction mixtureliquid was stirred at 120° C. for 60 minutes to react the titaniumcompound with mono-n-butyl phosphate. A white aqueous slurry of acatalyst containing the resultant reaction product was obtained. In thecatalyst slurry, the titanium content was 0.3% by mass and the molarratio M_(p)/M_(Ti) of the phosphorus element to the titanium element was2.0. As a result of further detailed analysis, it was confirmed that thecatalyst in the white slurry was a compound represented by the generalformula (III) wherein X represents a n-butyl group. This catalyst willbe referred to as titanium catalyst B hereinafter.

Referential Example 3

Measurement of Visible Light Absorption Spectrum of Tinting Agent

Preparation of Tinting Agents

A solution of each coloring matter shown in Table 1 in chloroform wasprepared in a concentration of 20 mg/liter at room temperature, and aquartz cell having an optical path length of 1 cm was filled with thesolution. A reference cell was filled with chloroform alone. The celland the reference cell were subjected to a measurement of visible lightabsorption spectra in a visible light wavelength band of from 380 to 780nm by using a spectrophotometer, model: U-3010, made by K.K. HitachiSeisakusho. In the case where two tinting agents are used in mixturethereof, the total concentration was adjusted to 20 mg/liter. The ratioof an absorbance of each solution at a wavelength of 400, 500, 600 or700 nm to an absorbance of each solution at a maximum absorptionwavelength was calculated. Also, the thermal mass reduction-initiatingtemperature of each tinting agent in the form of a powder was measured.The measurement results are shown in Table 1.

In the examples and comparative examples, in which the tinting agent wasadded to the polyester polymer during the production procedure of thepolyester polymer, the tinting agent was dissolved or dispersed in aconcentration of 0.1% by mass in a glycol solution used as a startingmaterial at a temperature of 100° C. TABLE 1 Mass Maximum reduction-absorption initiating Mixing wavelength Absorbance ratio*¹ temperatureType of tinting agent Ratio nm 400 nm 500 nm 600 nm 700 nm (° C.)Tinting agent A C.I. Solvent Blue 45 C.I. Solvent 60:40 580 0.10 0.410.76 0.00 360 (made by Clariant Japan) Violet 36 *2 B C.I. Solvent Blue45 C.I. Solvent 80:20 580 0.12 0.35 0.78 0.00 380 (made by ClariantJapan) Red 52 *2 C C.I. Solvent Red 52 — 100:0  580 0.28 0.93 0.03 0.00440 *2 D C.I. Solvent Green 20 — 100:0  685 0.25 0.06 0.48 0.98 400 *2*¹Ratio of absorbance at each specified wavelength to absorbance atmaximum absorption wavelength*2 Made by ARIMOTO KAGAKU K.K.

Example 1

(1) Preparation of Polyester Resin Composition Chips

A mixture of 100 parts by mass of dimethyl terephthalate with 70 partsby mass of ethylene glycol and 0.016 part by mass of the titaniumcatalyst A prepared in Referential Example 1 were charged in a SUSreactor for high pressure reaction. The mixture in the reactor wassubjected to an esterification reaction under a pressure of 0.07 MPawhile increasing the temperature of the reaction mixture from 140° C. to240° C., then 0.023 part by mass of triethyl phosphonoacetate was addedto the reaction mixture, and the reaction was mixed into the resultantreaction product, 0.2 part by mass of an ethylene glycol solution of0.1% by mass of the tinting agent (A) as shown in Table 1 was mixed. Theresultant reaction mixture was placed in a polymerization reactor andsubjected to a polycondensation reaction by increasing the temperatureof the reaction mixture to 290° C. under a high vacuum of 30 Pa or less.A tinted polyester resin composition having an intrinsic viscosity of0.63 and a diethyleneglycol content of 1.3% by mass was obtained. Thetinted polyester resin composition was formed into chips.

The test results are shown in Tables 2 and 3.

(2) Production of Polyester Fibers

The tinted polyester resin composition chips were dried at 160° C. for 4hours and then subjected to a melt-spinning procedure at a melt-spinningtemperature of 285° C., at a taking-up speed of 400 m/minute, to produceundrawn filament yarn having a yarn count of 333 Dtex/36 filaments. Theundrawn filament yarn was drawn at a draw ratio of 4.0 to produce adrawn filament yarn having a yarn count of 83.25 dtex/36 filaments. Atubular knitted fabric was produced from the drawn filament yarn. Thetest results are shown in Table 4.

(3) Production of Polyester Film

The tinted polyester resin composition chips were dried at 160° C. for 4hours, and melted at 285° C. The melt was extruded onto a rotatingcasting drum to form a sheet. In this case, the casting drum surface hada temperature of 30° C. immediately before the extruded melt was castedthereon, and then the surface temperature was gradually increased to 40°C. Also, an electrode in the form of a wire was arranged in contact witha surface of the melt sheet casted on the casting drum, opposite to thesurface of the melt sheet in contact with the casting drum surface,immediate after the melt was casted on the casting drum. Using theelectrode, the sheet of the polyester resin composition was staticallycharged to cause the sheet to be closely contact with the casting drum.As a result, an undrawn polyester film having a thickness of 500 μm wasobtained. The test results are shown in Table 4.

(4) Production of Polyester Resin-molded Article

(Production of Bottle Preform)

The tinted polyester resin composition chips were dried and crystallizedat 160° C. for 4 hours and then placed in a packed column type solidphase polymerization column. The dried chips were subjected to a solidphase polycondensation reaction in a nitrogen gas stream at 215° C. Theintrinsic viscosity of the chips was adjusted to 0.76 by controlling thepolymerization time. The solid phase polymerized chips wereinjection-molded by an injection molding machine at a cylindertemperature of 275° C. at a screw revolution number of 160 rpm, in aprimary pressurizing time of 3.0 seconds at a mold-cooling temperatureof 10° C., at a cycling time of 30 seconds. A cylindrical perform havingan outside diameter of about 28 mm, an inside diameter of 19 mm, alength of 136 mm, a body wall thickness of 4 mm and a mass of about 56 gwas obtained. The test results are shown in Table 4.

Example 2

By the same procedures as in Example 1, a tinted polyester resincomposition was produced and then polyester fibers, a polyester film anda polyester bottle preform were produced from the tinted polyester resincomposition with the following exceptions.

In the preparation of the tinted polyester resin composition, the typeof tinting agent as shown in Table 2 was employed in an amount as shownin Table 2.

The test results are shown in Tables 3 and 4.

Example 3

By the same procedures as in Example 1, a tinted polyester resincomposition was produced and then polyester fibers, a polyester film anda polyester bottle preform were produced from the tinted polyester resincomposition with the following exceptions.

In the production of the polyester polymer, no triethyl phosphonoacetatewas employed and the type and amount of the tinting agent were changedto as shown in Table 2.

The test results are shown in Tables 3 and 4.

Example 4

By the same procedures as in Example 1, a tinted polyester resincomposition was produced and then polyester fibers, a polyester film anda polyester bottle preform were produced from the tinted polyester resincomposition with the following exceptions.

The tinted polyester resin composition was produced by the followingprocedures.

In a reactor which contained a polyester oligomer in an amount of 225parts by mass, a slurry prepared by mixing 179 parts by mass of a highpurity terephthalic acid and 95 parts by mass of ethylene glycol, anitrogen gas, under conditions maintained at 255° C. under ambientatmospheric pressure, was fed at a constant supply rate. Anesterification reaction was carried out for 4 hours, while waterproduced by the reaction and ethylene glycol were removed from thereaction system by distillation, until the reaction was completed. Inthis reaction, the degree of esterification was 98% or more, and thedegree of polymerization of the resultant oligomer was approximately 5to 7.

The oligomer produced by the above-mentioned esterification reaction wasplaced in an amount of 225 parts by mass in a polycondensation reactionvessel. The oligomer in the reaction vessel was mixed with 1.5 parts bymass of the titanium catalyst B prepared in Referential Example 2 and0.32 part by mass of the a solution containing 0.1% by mass of thetinting agent (A) as shown in Table 1, dissolved in ethylene glycol.Subsequently, the reaction temperature in the reaction system wasincreased stepwise from 255° C. to 290° C. and the reaction pressure inthe reaction system was reduced stepwise from the ambient atmosphericpressure to a pressure of 30 Pa, to effect a polycondensation reaction,while removing water generated by the reaction and ethylene glycol fromthe reaction system to the outside thereof. As a result of the reaction,a tinted polyester resin composition having an intrinsic viscosity of0.63 and a diethylene glycol content of 1.3% by mass, was obtained. Thepolyester resin composition was formed into chips. The test results ofthe chips are shown in Table 3. Also, the test results of the shapedarticles produced from the chips are shown in Table 4.

Example 5

By the same procedures as in Example 4, a tinted polyester resincomposition was produced and then polyester fibers, a polyester film anda polyester bottle preform were produced from the tinted polyester resincomposition by the same procedures as in Example 1, with the followingexceptions.

In the preparation of the polyester polymer, the titanium catalyst B wasreplaced by the catalyst and the stabilizer as shown in Table 2. Thetest results are shown in Tables 3 and 4.

Example 6

By the same procedures as in Example 1, a tinted polyester resincomposition was produced and then polyester fibers were produced fromthe tinted polyester resin composition with the following exceptions.

In the preparation of the polyester polymer, dimethyl terephthalate usedas a starting material of the polycondensation was replaced by dimethyl2,6-naphthalene dicarboxylate. The resultant polyester polymer had anintrinsic viscosity of 0.60 and a diethylene glycol content of 1.0% bymass.

The polyester film and the polyester bottle preform were not produced.

Example 7

By the same procedures as in Example 1, a tinted polyester resincomposition was produced and then polyester fibers were produced fromthe tinted polyester resin composition with the following exceptions.

In the preparation of the polyester polymer, trimethylene glycol wasemployed in place of ethylene glycol and the polymerization temperaturewas charged from 290° C. to 265° C. Further, the titanium catalyst A wasreplaced by the catalyst as shown in Table 2. The resultant polyesterpolymer exhibited an intrinsic viscosity of 0.70.

Further, the melt-spinning temperature for the polyester fibers waschanged from 285° C. to 260° C. No polyester film and no polyesterbottle preform were produced.

The test results are shown in Tables 3 and 4.

Example 8

By the same procedures as in Example 1, a tinted polyester resincomposition was produced and then polyester fibers were produced fromthe tinted polyester resin composition with the following exceptions.

In the starting materials, dimethyl terephthalate was replaced bydimethyl 2,6-naphthalene dicarboxylate, and ethylene glycol was replacedby trimethylene glycol. Also, the polymerization temperature was changedfrom 290° C. to 265° C., and the titanium catalyst A was replaced by thecatalyst as shown in Table 2. The resultant polyester polymer had anintrinsic viscosity of 0.65.

In the production of the polyester fibers, the melt-spinning temperaturewas changed from 285° C. to 260° C. No polyester film and no polyesterbottle preform were produced.

The test results are shown in Tables 3 and 4.

Example 9

By the same procedures as in Example 1, a tinted polyester resincomposition was produced and then polyester fibers were produced fromthe tinted polyester resin composition with the following exceptions.

As a staring material, tetramethylene glycol was employed in place ofethylene glycol. The polymerization temperature was changed from 290° C.to 255° C. Also, the titanium catalyst A was replaced by the catalyst asshown in Table 2. The resultant polyester polymer exhibited an intrinsicviscosity of 0.70.

In the production of the polyester fibers, the melt-spinning temperaturewas changed from 285° C. to 260° C. No polyester film and no polyesterbottle preform were produced.

The test results are shown in Tables 3 and 4.

Example 10

By the same procedures as in Example 1, a tinted polyester resincomposition was produced and then polyester fibers were produced fromthe tinted polyester resin composition with the following exceptions.

In the staring materials, dimethyl 2,6-naphthalene dicarboxylate wasemployed in place of dimethyl terephthalate, and tetramethylene glycolwas used in place of ethylene glycol. The polymerization temperature waschanged from 290° C. to 265° C., and the titanium catalyst A wasreplaced by the catalyst as shown in Table 2. The resultant polyesterpolymer had an intrinsic viscosity of 0.65.

In the production of the polyester fibers, the melt-spinning temperaturewas changed from 280° C. to 260° C. No polyester film and no polyesterbottle preform were produced.

The test results are shown in Tables 3 and 4.

Comparative Example 1

By the same procedures as in Example 1, a tinted polyester resincomposition was produced and then polyester fibers, a polyester film anda polyester bottle preform were produced from the polyester resincomposition with the following exceptions.

The titanium catalyst A was replaced by the catalyst as shown in Table2. No tinting agent was contained in the polymer resin.

The test results are shown in Tables 3 and 4.

Comparative Examples 2 to 4

In each of Comparative Examples 2 to 4, by the same procedures as inExample 1, a tinted polyester resin composition was produced and thenpolyester fibers, a polyester film and a polyester bottle preform wereproduced from the tinted polyester resin composition with the followingexceptions.

The type and amount of the tinting agent were changed to as shown inTable 2.

The test results are shown in Tables 3 and 4.

Comparative Example 5

By the same procedures as in Example 1, polyester fibers, a polyesterfilm and a polyester bottle preform were produced from a tintedpolyester resin composition with the following exceptions.

The tinted polyester resin composition was prepared by the followingprocedures.

A mixture of 100 parts by mass of dimethyl terephthalate with 70 partsby mass of ethylene glycol, and 0.032 part by mass of manganese acetatetetrahydrate were charged in a reactor equipped with a stirrer, afractionating column and methyl alcohol-distillation condenser. Thetemperature of the reaction mixture in the reactor was graduallyincreased from 140° C. to 240° C., to effect a transesterificationreaction, while distilling and discharging methyl alcohol produced as aresult of the reaction to the outside of the reactor. To the reactionmixture liquid, 0.02 part by mass of trimethyl phosphate was added andthe transesterification reaction was ended.

The resultant reaction product was transferred from the reactor to areaction vessel equipped with a stirrer, a nitrogen gas inlet, apressure-reduction outlet and a distillation device. The reactionproduct was mixed with 0.045 part by mass of diantimony trioxide, andthe mixture was heated to a temperature of 290° C. and subjected to apolycondensation reaction under a high vacuum of 30 Pa or less. Apolyester resin containing no tinting agent was obtained. The sameforming tests as in Example 1 were carried out. The test results areshown in Tables 3 and 4. TABLE 2 Item TransesterificationPolycondensation Phosphorus Tinting agent Dicarboxylic catalyst catalystcompound Amount added acid Glycol Amount Amount Amount (Content) ExampleNo. component component Type (mmol %) Type (mmol %) Type (mmol %) Type(ppm by mass) Example 1 DMT EG Titanium 5 Titanium TEPA 20 Tinting 2catalyst A catalyst A agent A 2 DMT EG Titanium 5 Titanium TEPA 20Tinting 2 catalyst A catalyst A agent B 3 DMT EG Titanium 5 Titanium — —Tinting 5 catalyst A catalyst A agent A 4 DMT EG — — Titanium 7 — —Tinting 1.5 catalyst B agent A 5 DMT EG — — ALAA/LIA 15/10 — — Tinting 3agent A 6 DMN EG Titanium 5 Titanium TEPA 20 Tinting 2 catalyst Acatalyst A agent A 7 DMT TRMG TBT 30 TBT — — Tinting 2 agent A 8 DMNTRMG TBT 30 TBT — — Tinting 2 agent A 9 DMT TEMG TBT 40 TBT — — Tinting2 agent A 10 DMN TEMG TBT 40 TBT — — Tinting 2 agent A Compar- 1 DMT EGTitanium 5 Titanium — — — — ative catalyst A catalyst A Example 2 DMT EGTitanium 5 Titanium TEPA 20 Tinting 2 catalyst A catalyst A agent C 3DMT EG Titanium 5 Titanium TEPA 20 Tinting 2 catalyst A catalyst A agentD 4 DMT EG Titanium 5 Titanium TEPA 20 Tinting 12 catalyst A catalyst Aagent A 5 DMT EG MNA 25 SBO 30 TMP 28 — —

TABLE 3 Item Qualititative analysis result of metal components with aIntrinsic DEG Color Element contained (mmol %) true specific gravityM_(p)/M_(Ti) Example No. viscosity (wt %) L* a* b* Ti* P^($) Al Sb Mn of5.0 or more ratio Example 1 0.63 1.3 80.0 −6.7 1.9 5 15 0 0 0 Notdetected 3.0 2 0.63 1.3 79.5 −6.8 2.1 5 14 0 0 0 Not detected 2.8 3 0.631.3 73.0 −6.6 2.1 5 0 0 0 0 Not detected 0 4 0.63 1.3 80.5 −7.0 1.0 7 140 0 0 Not detected 2.0 5 0.63 1.3 79.0 −6.4 2.0 0 0 15 0 0 Not detected— 6 0.60 1.0 73.0 −5.5 2.7 5 16 0 0 0 Not detected 3.2 7 0.70 — 81.2−7.1 3.0 29 0 0 0 0 Not detected 0 8 0.65 — 75.0 −6.6 2.6 29 0 0 0 0 Notdetected 0 9 0.70 — 80.1 −7.2 −1.0 40 0 0 0 0 Not detected 0 10 0.65 —76.2 −6.6 0.2 39 0 0 0 0 Not detected 0 Comparative 1 0.63 1.3 81.5 −6.711.5 5 0 0 0 0 Not detected 0 Example 2 0.63 1.3 80.1 4.0 2.1 5 14 0 0 0Not detected 2.8 3 0.63 1.3 80.7 −11.3 3.5 5 14 0 0 0 Not detected 2.8 40.63 1.3 63.5 −3.5 −8.6 5 15 0 0 0 Not detected 3.0 5 0.63 0.7 73.5 −6.52.0 0 25 0 330^(&) 71^(&) Mn, Sb —

TABLE 4 Item Evaluation of polyester fibers Polyester Height of foreignPolyester bottle matter accumulation Color film preform Example No. onspinneret (μm) L* a* b* Haze (%) Haze (%) Example 1 3 95.2 −0.8 2.0 0.41.2 2 4 95.3 −0.7 2.1 0.5 1.2 3 3 92.0 −0.8 2.2 0.5 1.5 4 3 95.5 −0.81.2 0.4 1.3 5 5 94.8 −0.7 2.1 0.5 1.5 6 3 91.8 −0.6 2.6 — — 7 6 93.3−1.1 2.8 — — 6 3 92.1 −1.0 2.5 — — 9 4 93.2 −0.9 −1.1 — — 10 3 92.1 −0.80.1 — — Comparative 1 3 95.5 −0.7 10.4 0.3 1.3 Example 2 4 94.8 2.8 2.20.3 1.2 3 3 95.1 −6.5 3.6 0.4 1.4 4 3 86.4 −0.2 −7.6 0.6 2.1 5 55 92.1−0.8 2.1 2.1 7.2Notes of Table 2

DMT: Dimethyl terephthalate

DMN: Dimethyl 2,6-naphthalene dicarboxylate

EG: Ethylene glycol

TRMG: Trimethylene glycol

TEMG: Tetramethylene glycol

TBT: Tetra-n-butoxytitanium

MNA: Manganese acetate tetrahydrate

ALAA: Aluminum acetylacetonate

LIA: Lithium acetate

SBO: Diantimony trioxide

TEPA: Triethyl phosphonoacetate

TMP: Trimethyl phosphate

The amounts of transesterification catalyst, polycondensation catalystand phosphorus compound were respectively based on the molar amount ofDMT or DMN.

Notes of Table 3

DEG: Diethylene glycol

Color value (L*, a* and b* values) of polyester resin composition wasdetermined after the resin composition chips were heat-treated at 140°C. for two hours.

-   -   Ti*: Titanium element derived from a polyester-soluble titanium        compound contained in the polyester resin component.    -   P^(S): Phosphorus element contained in the polyester resin        composition

The contents of Al, Sb and Mn elements are in units of ppm by mass.

Ratio M_(P)/M_(Ti): A molar ratio of phosphorus element to titaniumelement contained in the catalyst in the aromatic polyester polymer.

The concentrations in m mole % of elements contained in the polyesterpolymer is determined per mole of the repeating units of the aromaticpolyester polymer.

Table 3 shows that the tinted polyester resin compositions of Examples 1to 10 according to the present invention had satisfactory compositionsand color values (L*, a* and b*) in practice, satisfactory fiber-formingproperty, film-forming property and injunction moldability in practiceand satisfactory performances for practice. Compared with them, thepolyester resin compositions of Comparative Examples 1 to 4 wereinsufficient in color (L*, a* and b*) and formability. Also, inComparative Example 5, the antimony compound was employed as a catalystand thus the resultant resin containing no tinting agent had ansatisfactory color. However, the resin contained a large amount ofresidual antimony and was unsatisfactory in the melt-spinning property.

Example 11

(1) Preparation of Polyester Resin Composition Chips

A mixture of 100 parts by mass of dimethyl terephthalate with 70 partsby mass of ethylene glycol and, as a transesterification catalyst, 0.032part by mass of manganese acetate tetrahydrate were charged in a reactorequipped with a stirrer, a fractionating column and a methylalcohol-distillation condenser. The resultant reaction mixture wasgradually heated from 140° C. to 240° C. to cause a transesterificationreaction to be carried out, while distill-removing methyl alcoholgenerated as a result of the reaction to the outside of the reactor. Theresultant reaction mixture liquid was mixed with 0.02 part by mass oftrimethyl phosphate and the transesterification reaction was ended. Theresultant reaction product was mixed with 0.3 parts by mass of anethylene glycol solution of 0.1% by mass of the tinting agent A as shownin Table 1, 1.5 parts by mass of an ethylene glycol slurry containing0.037 part by mass of diantimony trioxide (a polycondensation catalyst),and 20% by mass of titanium dioxide. The resultant reaction mixture wasplaced in a reaction vessel equipped with a stirrer, a nitrogengas-introduction inlet, a pressure reduction outlet and a distillationdevice. The temperature of the content in the reaction vessel wasincreased to 300° C., to effect a polycondensation reaction under a highvacuum of 30 Pa or less. As a result, a tinted polyester resincomposition, having an intrinsic viscosity of 0.73 and a diethyleneglycol content of 0.7% by mass, was obtained. The polyester resincomposition was formed into chips. Table 5 shows the starting materials,the catalyst and the additives of the tinted polyester resin compositionand Table 6 shows the test results thereof.

(2) Production of Polyester Fibers

The above-mentioned chips were dried at a temperature of 160° C. for 4hours, and the dried chips were subjected to a melt-spinning procedureunder the conditions of a temperature of 295° C. and a winding speed of400 m/minute, to prepare an undrawn filament yarn having a yarn count of333 dtex/36 filaments. The undrawn filament yarn was drawn at a drawnratio of 4.0, to prepare a drawn filament yarn having 83.25 dtex/36filament. A tubular knitted fabric produced from the drawn filament yarnwas subjected to the tests. The test results are shown in Table 6.

Examples 12 and 13

In each of Examples 12 and 13, a tinted polyester resin composition wasproduced and then polyester fibers were produced from the polyesterresin composition by the same procedures as in Example 11 with thefollowing exceptions.

In Example 12, the tinting agent A was replaced by the tinting agent Bas shown in Table 1, and in Example 13, the tinting agent was employedin an amount of 5 ppm by mass in place of 3 ppm by mass.

Example 14

By the same procedures as in Example 11, a tinted polyester resincomposition was produced and then polyester fibers were produced fromthe polyester resin composition with the following exception.

As a polycondensation catalyst, germanium dioxide (GEO) was employed inthe amount as shown in Table 5, in place of diantimony trioxide (SBO).The test results are shown in Table 6.

Example 15

By the same procedures as in Example 11, a tinted polyester resincomposition was produced and then polyester fibers were produced fromthe polyester resin composition with the following exceptions.

As shown in Table 5, dimethyl 2,6-naphthalene dicarboxylate was employedas a starting compound in place of dimethyl terephthalate. The resultantpolyester polymer had an intrinsic viscosity of 0.69 and a diethyleneglycol content of 0.6% by mass.

The test results are shown in Table 6.

Comparative Example 6

By the same procedures as in Example 11, a tinted polyester resincomposition was produced and then polyester fibers were produced fromthe polyester resin composition with the following exceptions.

No tinting agent was employed.

The test results are shown in Table 6.

Comparative Examples 7 to 9

In each of Comparative Examples 7 to 9, by the same procedures as inExample 11, a tinted polyester resin composition was produced and thenpolyester fibers were produced from the polyester resin composition withthe following exceptions.

The tinting agent (A) and the amount of the tinting agent were changedto as shown in Table 5.

The test results are shown in Table 6.

Example 10

By the same procedures as in Example 11, a tinted polyester resincomposition was produced and then polyester fibers were produced fromthe polyester resin composition with the following exceptions.

No tinting agent was employed and cobalt acetate tetrahydrate was addedin the amount as shown in Table 5.

The test results are shown in Table 6. TABLE 5 Item TransesterificationPolycondensation Phosphorus Titanium Cobalt Tinting agent Dicarboxyliccatalyst catalyst compound dioxide acetate Amount acid Amount AmountAmount Amount Amount (Content) Example No. component Type (mmol %) Type(mmol %) Type (mmol %) (% by mass) (mmol %) Type (ppm by mass) Example11 DMT MNA 25 SBO 25 TMP 28 0.3 — Tinting 3 agent A 12 DMT MNA 25 SBO 25TMP 28 0.3 — Tinting 3 agent B 13 DMT MNA 25 SBO 25 TMP 28 0.3 — Tinting5 agent A 14 DMT MNA 25 GEO 40 TMP 28 0.3 — Tinting 3 agent A 15 DMN MNA25 SBO 25 TMP 28 0.3 — Tinting 3 agent A Comparative 6 DMT MNA 25 SBO 25TMP 28 0.3 — — — Example 7 DMT MNA 25 SBO 25 TMP 28 0.3 — Tinting 3agent C 8 DMT MNA 25 SBO 25 TMP 28 0.3 — Tinting 3 agent D 9 DMT MNA 25SBO 25 TMP 28 0.3 — Tinting 12 agent A 10 DMT MNA 25 SBO 25 TMP 28 0.310 — —

TABLE 6 Item Resin composition chips Content of element Fibers IntrinsicDEG Color (ppm by mass) Color Example No. viscosity (wt %) L* a* b* SbGe Co Ti* L* a* b* Example 11 0.73 0.7 70.2 −5.2 6.5 245 0 0 1 or less90.1 −0.8 5.7 12 0.73 0.7 68.5 −5.4 6.8 248 0 0 1 or less 89.8 −0.9 6.013 0.73 0.7 66.9 −5.0 3.4 250 0 0 1 or less 89.0 −0.7 4.1 14 0.73 0.773.3 −5.7 6.4 0 81 0 1 or less 91.3 −1.0 5.8 15 0.69 0.6 66.1 −4.9 6.4220 0 0 1 or less 88.3 −0.7 5.7 Comparative 6 0.73 0.7 73.3 −5.3 10.7247 0 0 1 or less 91.5 −0.8 10.1 Example 7 0.73 0.7 70.4 5.1 6.6 250 0 01 or less 90.5 3.2 5.9 8 0.73 0.7 70.6 −13.1 6.9 252 0 0 1 or less 90.8−7.3 6.0 9 0.73 0.7 57.7 −3.3 −7.0 246 0 0 1 or less 84.4 −0.4 −6.8 100.73 0.7 70.1 −5.0 6.3 253 0 29 1 or less 89.9 −0.7 5.8Notes of Table 5

DMT: Dimethyl terephthalate

DMN: Dimethyl 2,6-naphthalene dicarboxylate

MNA: Manganese acetate tetrahydrate

SBO: Diantimony trioxide

GEO: Germanium dioxide

TMP: Trimethyl phosphate

Notes of Table 6

DEG: Diethylene glycol

Color L*, a* and b* values of the polyester resin composition chips weredetermined after the chips were heat-treated at 140° C. for 2 hours.

Ti*: Content of titanium metal element derived from titanium compoundcontained in the polyester resin composition and soluble in thepolyester. The Ti* value of 1 ppm by mass or less corresponds to thecontent of titanium metal element of 2×10⁻³% or less, on the basis ofthe total molar amount of all the dicarboxylic acids contained, as apolyester-constituting component in the polyester resin composition.

The contents of the transesterification catalyst, the polycondensationcatalyst, phosphorus compound and cobalt acetate were calculated on thebasis of the molar amount of DMT or DMN.

In Examples 11 to 15 according to the present invention, tintedpolyester resin compositions having good performances and polyesterfibers comprising the polyester resin composition were obtained.

The resin compositions of Comparative Examples 6 to 9 exhibited, whenformed into chips and fibers, unsatisfactory color.

In Comparative Example 10, the addition of the cobalt compound causedthe resultant polyester resin composition and fibers to exhibitexcellent color. However, due to too high a content of cobalt, theresultant polyester resin composition chips and fibers were insufficientin bleachability thereof.

Example 16

A mixture of 100 parts by mass of dimethyl terephthalate with 70 partsby mass of ethylene glycol and 0.016 part by mass of the titaniumcatalyst A prepared in Referential Example 1 were charged in a SUSvessel usable for reaction under pressurized conditions. The content inthe reaction vessel was heated from 140° C. to 240° C. under pressure of0.07 MPa, to effect a transesterification reaction. After it wasconfirmed that methyl alcohol was distill-removed in the stoichiometricamount from the reaction mixture, the transesterification reaction wadended.

Then the reaction product was transferred to a polymerization vessel,the content in the vessel was heated to a temperature of 290° C. toeffect the polycondensation reaction under a high vacuum of 30 Pa orless, while tracing the melt viscosity of the reaction mixture, and at astage at which the intrinsic viscosity of the resultant polyesterpolymer reached 0.65, the polymerization reaction was terminated. Apolymer melt was extruded in strand form from the bottom of the reactionvessel into cooling water, the cooled polymer strand was cut by using astrand cutter to prepare the polyester polymer chips. The test resultsare shown in Table 7.

The resultant aromatic polyester polymer chips were dried at 160° C. for4 hours and then fed into a two screw type extruder having a vent, inwhich extruder, a temperature of a kneading section was adjusted to 285°C., and in the kneading section the polymer chips were melted and mixedwith the tinting agent, as shown in Table 7 in a residing time of 5minutes. The tinted polymer was extruded in strand form into coolingwater, the resultant polymer strand was cut by a strand cutter, toprovide a polyester resin composition chips.

The test results are shown in Table 8.

Production of Polyester Fibers

The resultant polyester resin composition chips were dried at 160° C.for 4 hours, melt-spun at a melt-spinning temperature at 285° C. at awinding speed of 400 m/min., to provide undrawn filament yarn having ayarn count of 333 dtex/36 filaments, and then drawn at a draw ratio of4.0 to produce a drawn filament yarn having a yarn count of 83.25dtex/36 filaments. A tubular knitted fabric was produced from the drawnfilament yarn.

The test results are shown in Table 9.

Comparative Example 11

The same procedures as in Example 16 were carried out, except that notinting agent was mixed by melt-kneading.

The results are shown in Tables 7 to 9. TABLE 7 Item Base polymerCatalyst compound Phosphorus compound Tinting agent Intrinsic DEG AmountAmount Amount (Content) Example No Type viscosity (WT %) Type mmol %Type mmol % Type ppm by mass Example 16 PET 0.65 1.3 Titanium 5 — —Tinting 5 catalyst A agent A Comparative PET 0.65 1.3 Titanium 5 — — — —Example 11 catalyst A

TABLE 8 Item Quantitatic analysis result of metal Element contentcomponents with Intrinsic Color (mmol %) true specific gravityM_(p)/M_(Ti) Example No. viscosity L* a* b* Ti* P^($) Al Sb Mn of 5.0 ormore ratio^(#) Example 16 0.62 73.5 −6.2 2.6 5 0 0 0 0 Not detected 0Comparative 0.62 81.3 −6.4 12.1 5 0 0 0 0 Not detected 0 Example 11

TABLE 9 Item Evaluation result of polyester fibers Height ofaccumulation of foreign matter Color Example No. on spinneret (μm) L* a*b* Example 16 3 92.1 −0.7 2.4 Comparative 3 95.6 −0.7 11.0 Example 11Notes of Table 7

PET: Polyethyelene terephthalate

DEG: Diethylene glycol

The catalyst compounds and phosphorus compounds were added in theamounts (m mole %) based on the molar amount of DMT.

Notes of Table 8

The color of the polyester resin composition chips was measured afterheat-treating the chips at 140° C. for 2 hours.

-   -   Ti*: Concentration of metal elements contained in the polyester        resin composition and soluble in the resin composition.    -   $) P: Concentration of phosphorus element contained in the        polyester resin component    -   &) The contents of Sb, Mn element are in the units of ppm by        mass.    -   #) P/Ti ratio: Mollar ratio of phosphorus element to titanium        metal element contained in the catalyst in the aromatic        polyester polymer

The contents (m mole %) of elements in the aromatic polyester polymerwere calculated per mole of repeating units in the polymer.

In Example 16 according to the present invention, the polymer had a goodcolor even in the chip form and the yarn form. However, in ComparativeExample 11, the polymer was discolored yellowish in the chip form andthe yarn form and the polymer color was unsatisfactory.

Industrial Applicability

The tinted polyester resin composition of the present invention, and theshaped articles comprising the same, have good color and highapplicability to many uses.

1. A tinted polyester resin composition comprising an aromatic polyesterpolymer and a tinting agent, wherein (a) the tinting agent is present ina content of 0.1 to 10 ppm by mass, (b) a maximum absorption wavelengthof the tinting agent in an absorption spectrum in the wavelength rangeof 380 to 780 nm is in the range of 540 to 600 nm, determined in achloroform solution of the tinting agent in a concentration of 20mg/liter and at an optical path having a length of 1 cm, and (c) ratiosof optical absorbances A₄₀₀, A₅₀₀, A₆₀₀ and A₇₀₀ of visible lightspectra at wavelengths of 400 nm, 500 nm, 600 nm and 700 nm respectivelyto an optical absorbance A_(max) in the visible light spectrum at themaximum absorption wavelength, of the tinting agent, determined in theabove-mentioned chloroform solution of the tinting agent at the opticalpath having a length of 1 cm, satisfy the requirements (1) to (4):0.00≦A ₄₀₀ /A _(max)≦0.20  (1)0.10≦A ₅₀₀ /A _(max)≦0.70  (2)0.55≦A ₆₀₀ /A _(max)≦1.00  (3)0.00≦A ₇₀₀ /A _(max)≦0.05  (4)
 2. The tinted aromatic polyester resincomposition as claimed in claim 1, wherein the tinting agent is selectedfrom tinting coloring matters having a mass reduction-initiatingtemperature of 250° C. or more, determined by heating the coloringmatters in a nitrogen gas atmosphere at a temperature-increasing rate of10° C./minute while measuring the mass of the coloring matters by usinga thermobalance.
 3. The tinted aromatic polyester resin composition asclaimed in claim 1, wherein a cobalt metal element in the composition ispresent in a content controlled to 10 ppm by mass or less on the basisof the mass of the composition.
 4. The tinted aromatic polyester resincomposition as claimed in claim 1, wherein a metal element having a truespecific gravity of 5.0 or more, in the composition, is present in acontent controlled to 10 ppm by mass on the basis of the mass of thecomposition.
 5. The tinted aromatic polyester resin composition asclaimed in claim 1, wherein the aromatic polyester polymer is oneproduced by using a catalyst comprising at least one member selectedfrom titanium compounds and aluminum compounds.
 6. The tinted aromaticpolyester resin composition as claimed in claim 1, wherein the aromaticpolyester polymer is one produced by using a catalyst comprising atleast one member selected from titanium compounds and phosphoruscompounds; a molar ratio of phosphorus atoms to titanium atoms containedin the catalyst satisfies the requirement (5):1≦M _(p) /M _(Ti)≦15  (5) wherein M_(p) and M_(Ti) respectivelyrepresent contents in millimoles of phosphorus element and titaniumatoms contained in the aromatic polyester polymer; and the molar amountof the titanium metal element in the residual catalyst dissolved andcontained in the polyester resin composition is in the range of 2×10⁻³to 15×10⁻³% on the basis of the molar amount of all dicarboxylic acidscontained, as a polyester-constituting component, in the above-mentionedpolymer.
 7. The tinted aromatic polyester resin composition as claimedin claim 1, wherein the aromatic polyester polymer comprises, as aprincipal component, at least one member selected from the groupconsisting of polyethylene terephthalate, polyethylene naphthalate,polytrimethylene terephthalate, polytrimethylene naphthalate,polytetramethylene terephthalate and polytetramethylene naphthalate. 8.The tinted aromatic polyester resin composition as claimed in claim 1,wherein the tinting agent comprises a blue color-tinting coloring matterand a violet color-tinting coloring matter in a mass ratio in the rangeof from 90:10 to 40:60.
 9. The tinted aromatic polyester resincomposition as claimed in claim 1, wherein the tinting agent comprises ablue color-tinting coloring matter and a red or orange color-tintingcoloring matter in a mass ratio in the range of from 98:2 to 80:20. 10.The tinted aromatic polyester resin composition as claimed in claim 1,wherein the tinting agent is one mixed, at one or more stages in theproduction procedure of the aromatic polyester polymer, into a reactionmixture in the production procedure.
 11. The tinted aromatic polyesterresin composition as claimed in claim 1, wherein the tinting agent isone knead-mixed into the aromatic polyester polymer in the state of amelt.
 12. A tinted and shaped polyester resin article produced from thetinted polyester resin composition as defined in any one of claims 1 to11.
 13. The tinted and shaped polyester resin article as claimed inclaim 12, selected from fiber products.
 14. The tinted and shapedpolyester resin article as claimed in claim 12, selected from filmproducts.
 15. The tinted and shaped polyester resin article as claimedin claim 12, selected from bottle products.